WO2014175984A1

WO2014175984A1 - Polyolefin-soluble chromophores and processes for their production

Info

Publication number: WO2014175984A1
Application number: PCT/US2014/031461
Authority: WO
Inventors: Man Kit Ng; Patrick Brant; Donna J. Crowther; Hong Cheng; Patricia H. Kalamaras
Original assignee: Exxonmobil Chemical Patents Inc.
Priority date: 2013-04-24
Filing date: 2014-03-21
Publication date: 2014-10-30

Abstract

Described herein is a polyolefin-soluble chromophore, which can be described as comprising the reaction product of a terminally functionalized polyolefin having a Mn of at least 300g/mole; and a chromophore having a complementary functional moiety, or a chromophore-forming moiety; wherein a preferred terminally functionalized polyolefin is a vinyl-terminated polyolefin such as a vinyl-terminated propylene-oligomer, co-oligomer, polymer or copolymer, or ethylene-oligomer, co-oligomer or polymer. The vinyl-terminated polyolefin may be further functionalized to replace the vinyl group with a primary linker, forming the terminally functionalized polyolefin, then combined with a chromophore or a chromophore-forming moiety.

Description

TITLE: POLYOLEFIN-SOLUBLE CHROMOPHORES AND PROCESSES FOR THEIR PRODUCTION

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Application No. 61/815,554 filed April 24, 2013, the disclosure of which is herein incorporated by reference in its entirety.

FIELD OF THE INVENTION

[0002] The present invention(s) relate to solubilizing polar or charged chromophores in hydrophobic media, and more particularly to attaching chromophores to an oligomeric carrier to effectuate its solubility in a polymer, especially polyolefin, matrix.

BACKGROUND

[0003] Attaching small molecular weight chromophores to polymers is typically done by reaction in solvent. There is a problem when the desired polymer is non-polar, as chromophores are typically polar. Thus, the polymer must be somewhat polar or have high dielectric constant (e.g., polystyrene) to react in the same solvent together with the chromophore. Such limitations can be overcome in part by polymerization of polar monomers in the presence of the chromophore to attach the chromophore to the forming polymer, but this is typically limited to radical-type polymerization, and to a lesser extent, condensation and chain-growth polymerizations. There is a need to have the capability to attach a chromophore to very non-polar polyolefins made by cationic polymerization, while avoiding expensive grafting chemistry. In particular, grafting on polypropylene (and propylene copolymers) can be done by using maleic anhydride in the presence of a radical initiator under thermal conditions to provide anhydride groups along the polypropylene chain, but this is complex and expensive. The inventors have overcome these and other problems.

[0004] Some relevant publications include D.R. Robello in 28 J. POLY. Sci. PART A: POLY. CHEM. 1- 13 (1990); R. Bonnett et al. in 2(8) J. MATER. CHEM. 823-828 (1992); U. Lauter et al. in 16 MACROMOL. RAPID. COMMUN. 239-245 (1995); S.M. Burkinshaw et al. in 53 DYES AND PIGMENTS 229-235 (2002); E. Bucio et al. in 93 J. APPL. POLY. SCI. 172- 178 (2004); P.P.S. Lee et al. in 43 J. POLY. Sci. PART A: POLY. CHEM. 837-843 (2005); I.N. Fedulova et al. in 33(6) Russ. J. BiooRGANic CHEM. 589-593 (2007); P.J. Roth et al. in 43 MACROMOLECULES 895-902 (2010); and L. Liu et al. in 44 MACROMOLECULES 8614-8621 (201 1). SUMMARY

[0005] Described herein is a polyolefin-soluble chromophore comprising a hydrophilic chromophore chemically bonded to at least one terminal end of a polyolefin.

[0006] The invention(s) also include a polyolefin-soluble chromophore comprising (or consisting of) the reaction product of a terminally functionalized polyolefin having a number average molecular weight (Mn) of at least 300g/mole; and a chromophore having a complementary functional moiety.

[0007] The invention(s) also include a polyolefin-soluble chromophore comprising (or consisting of) the reaction product of terminally functionalized polyolefin having a Mn of at least 300g/mole having a terminal functionality, and a chromophore-forming moiety.

[0008] The invention(s) also include a process for forming a polyolefin-soluble chromophore comprising contacting a terminally functionalized polyolefin having a Mn of at least 300g/mole with a chromophore having a complementary functional moiety to form the polyolefin-soluble chromophore, or, alternately, contacting the terminally functionalized polyolefin with a chromophore-forming moiety.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 is a Ή NMR of an inventive atactic polypropylene-porphyrin (aPP- porphyrin) product;

[0010] Figure 2 is a UV/Vis spectra of this 4-arm aPP-porphyrin measured in cyclohexane at two concentrations;

[0011] Figure 3 is a NMR spectrum for tetrakis(aPP)-porphyrin product;

[0012] Figure 4 is a UV/Vis spectra of the 4-arm aPP-porphyrin in Figure 3 measured in cyclohexane at two concentrations;

[0013] Figure 5 is a UV/Vis spectra of neat aPP polymer and blend of 4-arm aPP- porphyrin with aPP (0.032 wt%); and

[0014] Figure 6 is a NMR spectrum for this aPP-Disperse Red ester.

DETAILED DESCRIPTION

[0015] This disclosure describes a concept and several approaches that can be used to link light-absorbing chromophores to polyolefins. The "terminally functionalized polyolefins" can be chain-end or side-chain functionalized polyisobutylene (PIB), poly(alpha- olefin) (PAO), polypropylene, poly(ethylene/propylene), poly(propylene/alpha-olefin) or poly(ethylene/alpha-olefin), among others, but preferably chain-end or "terminally" functionalized. Most preferably, the "polyolefins" or polyolefin portion of the vinyl or functionalized polymers referred to herein consist of ethylene or propylene with from 0 or 1 or 2 wt% to 10 or 20 or 30 or 40 or 50 wt% of a comonomer-derived group selected from ethylene (for propylene-based copolymers), C3 (for ethylene-based copolymers), and C₄ to C12 a-olefins. Preferably, styrenic moieties are absent from the polyolefins and functionalized polyolefins herein. The term "polyolefin" includes what may be referred to in the art as "oligomers" and "polymers", and are preferably linear as described further herein.

[0016] The chromophore-functionalized polyolefin may be used for a number of applications such as efficient, uniform dyeing of non-polar hydrophobic polymers (e.g., polypropylene fibers, plastics), colorimetric markers in performance fluids (lubricants), energy conversion in photovoltaics (PV), nanostructured assemblies, and anti-counterfeit markers. In the case of textile coloring, while the dyeing of naturally occurring polar materials (e.g., cotton, cellulose) and synthetic fibers (e.g., nylon, polyester, polyamide) are readily achieved with polar dye molecules or pigment (e.g., disperse type dye), the dyeing of nonpolar unmodified polymer (e.g., polypropylene) is much more difficult due to poor solubility and compatibility of the polar dye molecules in the polymer matrix. It is an objective of this approach that the polyolefin soluble dye molecules could replace or reduce the need for pigments in some applications. The inventive concept being disclosed is based on making dyes that can exhibit improved solubility/compatibility characteristics with polyolefin-based materials, but the invention may find other uses. For example, hydrocarbon soluble metal containing porphyrin and phthalocyanine molecules could be used for more effective catalytic reactions with hydrocarbons where the lack of catalyst solubility is overcome.

[0017] Typical chromophores are organic compounds that can absorb light in the visible spectrum region (400-700 nm) due to the presence of several molecular features including a chromophore and a pi-conjugated system (alternating arrangement of single and double bonds). Upon absorption of a photon, the new resonance structure of the conjugated system provides the visible color. Electron-donating (amino, hydroxyl, alkoxy, alkyl) and - withdrawing (nitro, cyano, sulfonate, ketone) groups are oftentimes present in the chromophore molecules for modifying the color and absorption intensity of the chromophore. The color of the chromophore being observed is the result of the complementary color of the wavelength being absorbed. Common chromophores found in organic dye structures are azo, methine, porphyrin, phthalocynaine, quinone, triarylmethane. For chromophores that contain ionic groups such as -SC^Na^-1-, the polymer to be dyed may need to be modified for dispersion of the dye molecules by forming ionic bonds. These are clearly limitations when a nonpolar hydrophobic polymer is used. The present invention(s) describe concepts and methods of covalently linking polyolefins to chromophores. Some representative chromophores are Disperse Red 1, Disperse Blue, porphyrin and phthalocyanine.

[0018] Two general approaches are illustrated herein by using chromophores that contain poly(conjugated) C=N linkages. The first approach involves a bond-forming process between functionalized chromophores with an appropriately functionalized polyolefin. Common functionalities that are useful include alcohol, phenol, halide, carboxylic acid, and alkene. These functional groups can participate in various high-yielding reactions such as esterification, etherification, amidation, amination, alkene cross-metathesis, carbon-carbon cross-coupling, etc. The second approach involves the construction of chromophore from polyolefin-containing moieties, as illustrated for the formation of meso-substituted porphyrin and phthalocyanine.

[0019] Examples of the first approach are functionalization of an existing chromophore with chain-end functionalized polyolefin, or "primary linker" (esterification, alkene cross metathesis, substitution, etc.), which reacts with a "complementary functional moiety" on the chromophore:

Disperse Red 1 polyolefin-Disperse Red Ester

Disperse Red 1 acrylate

polyolefin-Disperse Red Ester polyolefin O

-OH -polyolefin base polyolefin-0

phthalocyanine silicon dichloride

[0020] An example of the second approach involves the construction of a chromophore from polyolefin comprising chromophore-forming moieties, as illustrated for the formation of meso-substituted porphyrin and phthalocyanine. Tetra(polyolefin)-substituted porphyrin from macrocyclization of aldehyde-containing polyolefin with pyrrole, an example of a "chromophore-forming moiety":

polyolefin polyolefin-CHO

[0021] Tetra(polyolefin)-substituted phthalocyanine from macrocyclization of phthalonitrile-containing polyolefin, the phthalonitrile being another "chromophore-forming moiety":

[0022] In addition, formation of metal complex or introduction of heteroatoms to the center of the porphyrin or phthalocyanine ring can provide control of the color and polarity of the chromophore by shifting the absorption band.

[0023] Thus, the first approach to obtaining the polyolefin-soluble chromophore more generally comprises the reaction product of a terminally functionalized polyolefin and a chromophore having a complementary functional moiety. The "terminally functionalized polyolefin" comprises a polyolefin component and a functional component, or "primary linker" such as a vinyl group, an aldehyde group, a halogen, etc. Generally, the "primary linker" is a chemical group capable of reacting with the complementary functional moiety of the chromophore to form a chemical bond between the polyolefin and chromophore. Here and throughout, when referring to the "polyolefin", it is understood that it may have the characteristics as described in general for polyolefins, or more particularly, propylene-based polymers, as described throughout this specification. Also, by "complementary functional moiety," what is meant is a moiety attached to the chromophore that will react with the primary linker of the terminally functionalized polyolefin to form at least one covalent bond between the two to result in a new compound including the chromophore and polyolefin. Preferably, the "complementary functional moiety" comprises a vinyl, ester, ketone, aldehyde, carboxylate (and carboxylic acid), epoxy, anhydride, thiol, silane, hydroxyl, amine, or halogen group.

[0024] In any case, the "terminally functionalized polyolefin" can be any polyolefin, as described herein, having the primary linker at its terminal end which preferably comprises a vinyl, ester, ketone, aldehyde, carboxylate (and carboxylic acid), epoxy, anhydride, thiol, silane, hydroxyl, amine, or halogen group. Preferably, the useful functionalized polyolefin starts as a vinyl-terminated polyolefin (or polypropylene, etc.) and is either reacted directly with a chromophore having the complementary functional moiety or first reacted with a chemical compound to create the primary linker, such as listed above, which is then reacted with the chromophore or chromophore-forming moiety.

[0025] The second approach to obtaining the inventive polyolefin-soluble chromophore more generally comprises the reaction product of the terminally functionalized polyolefin and a chromophore-forming moiety. The "chromophore-forming moiety" is a chemical compound that can form a chemical bond to the terminally functionalized polyolefin and also serve to form a chromophore by also reacting with another chemical species, which can be another similar or same chemical species bound to another terminally functionalized polyolefin, to form a chromophore, that is, a compound absorbing light in the visible light spectrum. Thus, from 2 to 4 or 6 or 8 or more molar equivalents of the functionalized polyolefin may be contacted with the chromophore-forming moiety to form the reaction product, or various other molar ratios, depending on the nature of the chromophore-forming moiety. In any case, the polyolefin-soluble chromophore may further comprise the reaction product of a chromophore-forming moiety selected from pyrroles and mercaptoalkylacids; or, stated another way, the chromophore-forming moiety is a phthalonitrile or pyrrole. [0026] In any case, the chromophore can be any desirable chromophore known in the art. Preferred chromophores are selected from azobenzenes, anthroquinones, triphenylmethanes, phthalocynanines, trichlorotriazines, and porphyrins, wherein reference to the plural of these compounds means that they encompass the class of compounds that are substituted, where the chromophore may be substituted with one or more to alkyl groups, C₂ to C₁₄ alkene groups, to C 12 aryl groups, electron donating groups (e.g., hydroxyl, alkoxy, amino, alkylamine, chloride, bromide, iodide), electron withdrawing groups (e.g. nitro, cyano, sulfonate, ketone, fluoride, trihalomethyl, esters), or combinations thereof. Thus, for example, "azobenzenes" would include bromo-azobenzene, methyl-azobenzene, vinyl- azobenzene, etc.

[0027] Propylene-based polymers are particularly desirable as the polyolefin portion of the terminally functionalized polyolefins useful in the invention, as well as the chromophore- functionalized polyolefin itself. These polymers will also have a Mn of at least 300g/mole, or as described herein. The "propylene-based polymers" are those polymers that comprise greater than 50 wt% or 60 wt% or 70 wt% or 80 wt% propylene-derived units, and preferably comprise from 50 wt% or 60 wt% or 80 wt% to 95 wt% or 99 wt% or 100 wt% propylene- derived units, the remainder being ethylene or C₄ to C IQ a-olefin-derived units. Desirable propylene-based polymers include homopolymers, copolymers, elastomers, impact copolymers, block copolymers, isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof. Any of these may be vinyl-terminated, as described below, and/or may contain multiple vinyl groups pendant to the polymer chain.

[0028] Preferably, the terminally functionalized polyolefins described herein are vinyl- terminated polyolefins, and more particularly, vinyl-terminated propylene-based polymers. As described herein, "vinyl-terminated polyolefins", "vinyl-terminated propylene-based polymers" and other "vinyl-terminated polymers" are polymers as first described in US 2009/0318644 having at least one terminus (CH₂CH-CH2-oligomer or polymer) represented by formula (I):

allylic vinyl end group where the ^» represents the oligomer or polymer chain. In a preferred embodiment the allyl chain ends are represented by the formula (II):

The amount of allyl chain ends is determined using NMR at 120°C using deuterated tetrachloroethane as the solvent on a 500 MHz machine, and in selected cases confirmed by ¹³C NMR. These groups (I) and (II) will react to form a chemical bond with a metal as mentioned above to form the M— CH2CH2— polymer. In any case, Resconi has reported proton and carbon assignments (neat perdeuterated tetrachloroethane used for proton spectra while a 50:50 mixture of normal and perdeuterated tetrachloroethane was used for carbon spectra; all spectra were recorded at 100°C on a Bruker AM 300 spectrometer operating at 300 MHz for proton and 75.43 MHz for carbon) for vinyl-terminated propylene polymers in Resconi et al, 1 14 J. AM. CHEM. SOC. 1025- 1032 (1992) that are useful herein.

[0029] The vinyl-terminated propylene-based polymers may also contain an isobutyl chain end. "Isobutyl chain end" is defined to be an oligomer having at least one terminus represented by the formula (III):

In a preferred embodiment, the isobutyl chain end is represented by one of the following formulae:

The percentage of isobutyl end groups is determined using ¹³C NMR (as described in the example section) and the chemical shift assignments in Resconi for 100% propylene oligomers. Preferably, the vinyl-terminated polymers described herein have an allylic terminus, and at the opposite end of the polymer an isobutyl terminus.

[0030] The vinyl-terminated polyolefin can be any polyolefin having a vinyl-terminal group as described above for the vinyl-terminated polypropylenes, and is preferably selected from the group consisting of vinyl-terminated isotactic polypropylenes, atactic polypropylenes, syndiotactic polypropylenes, and propylene-ethylene copolymers (random, elastomeric, impact and/or block), and combinations thereof, each having a Mn of at least 300g/mole. Preferably, greater than 90 or 94 or 96% of the vinyl-terminated polyolefin comprises terminal vinyl groups; or within the range of from 10 or 20 or 30% to 50 or 60 or 80 or 90 or 95 or 98 or 100%. As described above, the vinyl-terminated polyolefins have a Mn value of at least 300 or 400 or 1000 or 5000 or 20,000 g/mole, or within the range of from 300 or 400 or 500g/mole to 20,000 or 30,000 or 40,000 or 50,000 or 100,000 or 200,000 or 300,000g/mole. The functionalized, or vinyl-terminated polyolefin, and preferably, vinyl- terminated propylene-based polymer, is preferably linear, meaning that there is no polymeric or oligomeric branching from the polymer backbone, or alternatively, having a branching index "g", as is known in the art, of less than 1 or 0.9 or 0.8 or 0.7 or most preferably less than 0.6, wherein the "branching index" is well known in the art and measurable by published means, and the value of such branching index referred to herein within 10 or 20% of the value as measured by any common method of measuring the branching index for polyolefins as is known in the art.

[0031] The description for the "vinyl termination polyolefin" is also consistent for terminally functional polyolefins in that the polyolefin portion of such polymers, whether terminated with a vinyl group or some other functional moiety, primary linker, etc., will have the similar amount of terminal groups as vinyl groups and the same molecular weight, branching, etc. This is also true for the polyolefin portion that is a propylene-based polymer.

[0032] The inventive polyolefin-soluble chromophores may have many uses not mentioned here. As an example of desirable applications, they may be useful in photovoltaic cells where the chromophore is a light-gathering center for charge separation or other generation of an electric current. Such light-gathering centers may advantageously be fixed in a hydrophobic polymer matrix such as a polyethylene or polypropylene-based film, sheet or surface. The polyolefin-soluble chromophores described herein may also be useful as a colorimetric marker for paper, synthetic fabric or sheets, organic or biological fluids, or natural fibers and fabrics. There is often a need to add light-absorbing functionality or aesthetic appeal to various hydrophobic or partially hydrophobic media, and the inventive polyolefin-soluble chromophores would be suitable for such applications. Also, the polyolefin-soluble chromophore could be suitable as a catalyst in hydrophobic media, wherein the chromophore may optionally be a catalyst such as an organic, organometallic or metal-complex that not only absorbs light, but the primary function of which is as a catalyst for desirable chemical transformations.

[0033] The polyolefin-soluble chromophore as described can be made by any suitable method. Preferably, the invention includes a process for forming a polyolefin-soluble chromophore comprising contacting a vinyl-terminated polyolefin, preferably a vinyl- terminated polypropylene, with a functionalizing agent to form a terminally functionalized polyolefin comprising a primary linker; then contacting the terminally functionalized polyolefin comprising a primary linker with a chromophore having a complementary functional moiety or a chromophore-forming moiety; and finally isolating the polyolefin- soluble chromophore. The terminally functionalized polyolefin need not be specifically purified or separated from the initial reaction product mixture, though it can be, and the same is true for the final terminally functionalized polyolefin before its use in blending with polyolefins such as polyethylene, polypropylene, polystyrene or other hydrophobic polymers. The "contacting" should take place under conditions to effectuate the formation of chemical bonds as claimed, as exemplified in the working examples. Preferably, the components are contacted in a solvent system (single solvent or mixture of solvents) having a dielectric constant of less than 18 or 16 or 12 or 10 or 8 or 6 or 5, measured such that, as standards to within 10% of the value, the same method of measurement results in a dielectric constant (25°C) of N-methylpyrrolidone of 32.2, THF of 7.5, benzene of 2.3, and cyclohexane of 2.0.

[0034] In the inventive process, the chromophore is preferably based on azobenzenes, phthalocyanines, porphyrins, or combinations thereof. By "based on", what is meant is that the chromophore molecules may have pendant substitutions such as electron withdrawing or donating groups as is known in the art, and may also include a complimentary functional group attached at any point on the chromophore. Preferably, the chromophore-forming moiety is based on pyrrols or mercaptoalkylacids, or combinations thereof, the term "based on" having the same meaning as for the chromophore. Also, the functionalizing agent is preferably any agent capable of reacting with a vinyl group to form ester, ketone, aldehyde, carboxylate (and carboxylic acid), epoxy, anhydride, thiol, silane, hydroxyl, amine, or halogen primary linker. Examples of such agents, such as hydroformylation agents or brominating agents, are demonstrated in the working examples but are well known to those in the art. [0035] The various descriptive elements and numerical ranges disclosed herein for the polyolefin-soluble chromophore, and method of making them, can be combined with other descriptive elements and numerical ranges to describe the invention(s); further, for a given element, any upper numerical limit can be combined with any lower numerical limit described herein. The features of the invention are described in the following non-limiting examples.

EXAMPLES

[0036] Example 1 : Synthesis of aldehyde-modified atactic polypropylene (aPP-CHO) by hydroformylation of vinyl-terminated atactic polypropylene (vt aPP):

aPP-CHO

Synthesis of 5,10, 15,20-tetrakis(polypropylene)porphyrin by acid-catalyzed macrocyclization of aPP-aldehyde with pyrrole:

(aPP: atactic polypropylene)

[0037] To a solution of atactic polypropylene aldehyde (NB No. 25723-48-3, formyl group content approx. 0.944 mmol/g, 2.48g, 2.34 mmol) and pyrrole (0.157g, 2.34 mmol) in methylene chloride (234 ml) was added a stock solution of boron trifluoride diethyl etherate in methylene chloride (0.469 M, 0.499 ml, 0.234 mmol) at room temperature under a nitrogen atmosphere. The resulting dark mixture was stirred at room temperature for 1.5 hours and tetrachloro-l,4-quinone (0.575g, 2.34 mmol) was added. Stirring was continued for an additional 1.5 hours at room temperature. This was followed by addition of triethylamine (0.095g, 0.939 mmol). The solution was concentrated on a rotary evaporator under reduced pressure and the crude product was purified on S1O2 using hexanes/methylene chloride as eluent. The desired tetrakis(aPP)-substituted porphyrin fraction was obtained as a dark purple viscous oil. ^lR NMR spectrum (400 MHz, CDCI3) shows Ar-CH₂-(aPP) absorption signal at 4.92 ppm and ring NH at -2.60 ppm. This tetrakis(aPP)-porphyrin product has NB No. 26277-073 and a purity of about 70 to 80%. The major impurities are unreacted starting materials and not likely to exhibit absorption in the visible light region. A NMR spectrum for the aPP-porphyrin is shown in Figure 1. Impurity peaks appearing at about δ 9.6 ppm (CDCI3) can be identified.

[0038] UV/Vis spectra of this 4-arm aPP-porphyrin measured in cyclohexane at two concentrations (0.016 and 0.3g/L for highlighting different absorption region) are shown in Figure 2. The Soret band (400, 418 nm) and Q bands (521, 553, 602, 652 nm) characteristic of the light-absorbing porphyrin ring are clearly observed.

[0039] Example 2: Synthesis of aPP-bromide by hydrohalogenation of vt aPP:

[0040] To a solution of vinyl-terminated atactic polypropylene (NB No. 25826-027-002, !H NMR M_n about 1866g/mol, lOO.OOg, 53.6 mmol) in hexanes (120 ml) cooled to -10°C was added dropwise a mixture of 33 wt% hydrogen bromide in acetic acid (18.75 ml, 103 mmol) and hexanes (20 ml) for over 30 minutes. After complete addition, the resulting mixture was stirred at -10°C for an additional 20 minutes and then at 0°C for 1.5 hours. Ice- cold water (200 ml) was added to the mixture and the aqueous phase was extracted with hexanes. The organic extract was washed with water, brine, dried over MgS0₄, filtered and concentrated on a rotary evaporator to give a clear and colorless liquid (100.34g). This aPP- bromide product has NB No. 26228-081.

[0041] Synthesis of 5,10,15,20-tetrakis[4-(polypropylene)oxyphenyl]porphyrin by alkylation with aPP-bromide:

[0042] A mixture of 5, 10, 15,20-tetrakis(4-hydroxyphenyl)porphyrin (0.58 lg, 0.856 mmol), atactic polypropylene bromide (NB No. 26228-081, ^lR NMR M_n about 1947g/mol, 8.00g, 4.1 1 mmol), potassium carbonate (0.71g, 5.14 mmol) and potassium iodide (0.028g, 0.169 mmol) in tetrahydrofuran (75 ml) and N-methylpyrrolidinone (15 ml) was heated at reflux for 48 hours under a nitrogen atmosphere. The resulting dark purple solution was concentrated under reduced pressure. The residue was diluted with hexanes, washed with water and brine. The organic layer was separated, dried ( a₂S04), filtered and excess solvent was removed on a rotary evaporator under reduced pressure to afford a dark purple viscous oil as crude product (9.5g). This crude product was dissolved in hexanes and purified on silica gel (hexanes gradient to hexanes/ethyl acetate as eluent) to afford a dark purple viscous oil (5.6g). This tetrakis(aPP)-porphyrin product has NB# 26228-082. A ^lR NMR spectrum for this aPP-porphyrin is shown in Figure 3.

[0043] UV/Vis spectra of this 4-arm aPP-porphyrin measured in cyclohexane at two concentrations (0.014 and 0.29g/L) are in Figure 4. The Soret band (400, 420 nm) and Q bands (516, 553, 596, 653 nm) are clearly observed. The minor shift in absorption maxima is presumably due to the presence of a phenoxy linker between the aPP chain and the porphyrin ring.

[0044] Dyeing of aPP polymer with aPP-porphyrin dye: The uniform dyeing of an amorphous polypropylene liquid with the synthesized tetrakis(aPP)-porphyrin (NB No. 26228-082) was demonstrated by physically mixing (blending) the porphyrin with a colorless aPP liquid (Mn about lOOOg/mol) at about 40 to 50°C at two different dye concentrations. It was clear from visual inspection that homogeneous dyeing was achieved with aPP-porphyrin loading of 0.032 wt% (left, light yellowish brown) or 0.5 wt% (right, purple), respectively at room temperature. UV/Vis spectra of neat aPP polymer and blend of 4-arm aPP-porphyrin with aPP (0.032 wt%) is shown in Figure 5. The Soret band and Q bands (516, 553, 597, 653 nm) are clearly observed.

[0045] Example 3 : Synthesis of carboxylic acid-terminated aPP (26277-077) by thiol-ene addition

hv -365 nm

hydrothiolation [0046] A mixture of vinyl-terminated atactic polypropylene (NB No. 25826-027-002, NMR M_n about 1866g/mol, 8.00g, 4.29 mmol), 3-mercaptopropionic acid (0.523g, 4.93 mmol) and 2,2-dimethoxy-2-phenylacetophenone (0.01 lg, 0.0429 mmol) in benzene (6 ml) was irradiated with a UV lamp (4 W, 365 nm) at room temperature for 10 minutes. The resulting homogeneous colorless solution was diluted with hexanes (40 ml), washed with water and brine. The organic layer was separated, dried (Na₂S04), filtered and excess solvent was removed on a rotary evaporator under reduced pressure to afford a colorless liquid as crude product. This crude product was further heated under high vacuum at 80°C to afford a colorless viscous oil (7.97g). This aPP-carboxylic acid product has NB No. 26277-

077.

[0047] Synthesis of Disperse Red-linked atactic polypropylene (26277-079) by esterification of Disperse Red 1 with aPP-carboxylic acid (26277-077):

Disperse Red 1 aPP-Disperse Red Ester

[0048] To a solution of atactic polypropylene carboxylic acid (NB# 26277-077, ^lK NMR M_n about 1972g/mol, 3.05g, 1.55 mmol), Disperse Red 1 (0.535g, 1.70 mmol) and 4-

(dimethylamino)pyridine (0.0283g, 0.232 mmol) in methylene chloride (14 ml) was added dicyclohexylcarbodiimide (0.383g, 1.86 mmol) at room temperature. The resulting dark red mixture was stirred at room temperature for 14 hours. The mixture was filtered and the filtrate concentrated to afford a dark red crude product. This crude product was dissolved in hexanes and purified on silica gel (hexanes gradient to hexanes/ethyl acetate as eluent) to afford a dark red viscous oil. This product has NB No. 26277-079. A NMR spectrum for this aPP-Disperse Red ester is shown in Figure 6.

[0049] Having described the various features of the polyolefin-soluble chromophore and methods of making it, described here in numbered embodiments is:

1. A polyolefin-soluble chromophore comprising a hydrophilic chromophore chemically bonded to at least one terminal end of a polyolefin. The polyolefin-soluble chromophore of numbered embodiment 1, wherein the polyolefin is selected from propylene-based oligomers, co-oligomers, polymers and copolymers, and ethylene-based oligomers, co-oligomers, polymers and copolymers. The polyolefin-soluble chromophore of numbered embodiment 1 or 2, wherein the terminally functionalized polyolefin has an Mn of at least 300 or 400 or 500 or 1000 or 20,000g/mole; or a Mn within the range of from 300 or 500 or 800g/mole to 1400 or 1600 or 1800 or 2000 or 2200 or 3000g/mole.

The polyolefin-soluble chromophore of any one of the previous numbered embodiments, where the polyolefin-soluble chromophore comprising the reaction product of:

a terminally functionalized polyolefin having a Mn of at least 300g/mole; and a chromophore having a complementary functional moiety or a chromophore-forming moiety.

The polyolefin-soluble chromophore of any one of the previous numbered embodiments, wherein the terminally functionalized polyolefin comprises a vinyl, ester, ketone, aldehyde, carboxylate (and carboxylic acid), epoxy, anhydride, thiol, silane, hydroxyl, amine, or halogen primary linker.

The polyolefin-soluble chromophore of any one of the previous numbered embodiments, further comprising the reaction product with a chromophore-forming moiety selected from pyrroles and mercaptoalkylacids.

The polyolefin-soluble chromophore of any one of the previous numbered embodiments, wherein the chromophore is selected from azobenzenes, anthroquinones, triphenylmethanes, phthalocynanines, trichlorotriazines, and porphyrins.

The polyolefin-soluble chromophore of any one of the previous numbered embodiments, wherein the terminally functionalized polyolefin comprises a terminal functionality (primary linker) and a polyolefin, wherein the polyolefin is selected from polyethylenes, polypropylenes, ethylene-propylene copolymers, and combinations thereof, (e.g., C3C4, C^C^, C^Cg, 03( 0, C3Q2, C3Q4, C^Ci^).

The polyolefin-soluble chromophore of any one of the previous numbered embodiments, wherein the terminally functionalized polyolefin has a Mn within the range of from 300 or 500 or 800g/mole to 1400 or 1600 or 1800 or 2000 or 2200 or 3000g/mole. The polyolefin-soluble chromophore of any one of the previous numbered embodiments, wherein the terminally functionalized polyolefin is a vinyl-terminated polyolefin, or a vinyl-terminated polyolefin that has been further functionalized with a primary linker or a chromophore-forming moiety.

The polyolefin-soluble chromophore of any one of the previous numbered embodiments, wherein the components are reacted in a solvent system (single solvent or mixture of solvents) having a dielectric constant of less than 18 or 16 or 12 or 10 or 8 or 6 or 5.

A photovoltaic cell comprising the polyolefin-soluble chromophore of any one of the previous numbered embodiments.

A colorimetric marker for paper, synthetic fabric or sheets, organic or biological fluids, or natural fibers and fabrics comprising the polyolefin-soluble chromophore of any one of the previous numbered embodiments.

A catalyst for hydrophobic media comprising the polyolefin-soluble chromophore of any one of the previous numbered embodiments.

A process for forming a polyolefin-soluble chromophore of any one of the previous numbered embodiments comprising contacting the terminally functionalized polyolefin having a Mn of at least 300g/mole with a chromophore having a complementary functional moiety or a chromophore-forming moiety to form the polyolefin-soluble chromophore.

The process of numbered embodiment 15, wherein the contacting results in a chemical reaction selected from esterification, etherification, amidation, amination, alkene cross-metathesis, carbon-carbon cross-coupling, elimination, addition (e.g., addition of a thiol group across a carbon-carbon double bond) substitution, or combinations thereof.

The process of numbered embodiments 15 or 16, wherein a vinyl-terminated polyolefin, comprising a vinyl group at its terminal end of the chain, is transformed to comprise a primary linker to form the functionalized polyolefin.

The process of any one of numbered embodiments 15 to 17, wherein the polyolefin is selected from propylene-based oligomers, co-oligomers, polymers and copolymers, and ethylene-based oligomers, co-oligomers, polymers and copolymers.

The process of any one or previous embodiments 15 to 18, wherein the components are contacted in a solvent system (single solvent or mixture of solvents) having a dielectric constant of less than 18 or 16 or 12 or 10 or 8 or 6 or 5. 20. A process for forming a polyolefin-soluble chromophore of any one of the numbered embodiments comprising:

a. contacting a vinyl-terminated polyolefin, preferably a vinyl-terminated polypropylene, with a functionalizing agent to form a terminally functionalized polyolefin comprising a primary linker;

b. contacting the terminally functionalized polyolefin comprising a primary linker with a chromophore having a complementary functional moiety or a chromophore-forming moiety; and

c. isolating the polyolefin-soluble chromophore.

21. The process of numbered embodiment 20, wherein the chromophore is based on azobenzenes, phthalocyanines, porphyrins, or combinations thereof.

22. The process of numbered embodiments 20 or 21, wherein the chromophore-forming moiety is based on pyrrols or mercaptoalkylacids, or combinations thereof.

23. The process of any one of numbered embodiments 20 to 22, wherein the functionalizing agent is any agent capable of reacting with a vinyl group to form ester, ketone, aldehyde, carboxylate (and carboxylic acid), epoxy, anhydride, thiol, silane, hydroxyl, amine, or halogen primary linker.

[0050] The invention also includes the use of a vinyl-terminated polyolefin in forming a polymer soluble chromophore by the process of numbered embodiment 20.

[0051] The invention also includes the use of a polyolefin-soluble chromophore in any one of the numbered embodiments 1 through 1 1 as a marker for paper, synthetic fabric or sheets, organic or biological fluids, or natural fibers and fabrics, or in a photovoltaic cell, or as a catalyst.

Claims

1. A polyolefin-soluble chromophore comprising a hydrophilic chromophore chemically bonded to at least one terminal end of a polyolefin.

2. The polyolefin-soluble chromophore of claim 1, wherein the polyolefin is selected from propylene-based oligomers, co-oligomers, polymers and copolymers, and ethylene- based oligomers, co-oligomers, polymers and copolymers.

3. The polyolefin-soluble chromophore of claims 1 or 2, wherein the polyolefin portion has a Mn within the range of from 300 or 500 or 800g/mole to 1400 or 1600 or 1800 or 2000 or 2200 or 3000g/mole.

4. A polyolefin-soluble chromophore comprising the reaction product of:

a terminally functionalized polyolefin having a Mn of at least 300g/mole; and a chromophore having a complementary functional moiety.

5. The polyolefin-soluble chromophore of claim 4, wherein the terminally functionalized polyolefin comprises a vinyl, ester, ketone, aldehyde, carboxylate (and carboxylic acid), epoxy, anhydride, thiol, silane, hydroxyl, amine, or halogen primary linker.

6. The polyolefin-soluble chromophore of claim 5, further comprising the reaction product with a chromophore-forming moiety selected from pyrroles and mercaptoalkylacids.

7. The polyolefin-soluble chromophore of claims 4 or 5, wherein the chromophore is selected from azobenzenes, anthroquinones, triphenylmethanes, phthalocynanines, trichlorotriazines, and porphyrins.

8. The polyolefin-soluble chromophore of any one of claims 4 to 7, wherein the terminally functionalized polyolefin comprises a primary linker and a polyolefin, wherein the polyolefin is selected from polyethylenes, polypropylenes, ethylene-propylene copolymers, and combinations thereof.

9. The polyolefin-soluble chromophore of any one of claims 4 to 8, wherein the terminally functionalized polyolefin has an Mn within the range of from 300 or 500 or 800 g/mole to 1400 or 1600 or 1800 or 2000 or 2200 or 3000 g/mole.

10. The polyolefin-soluble chromophore of any one of claims 4 to 9, wherein the terminally functionalized polyolefin is a vinyl-terminated polyolefin, or a vinyl-terminated polyolefin that has been further functionalized with a primary linker or a chromophore- forming moiety.

1 1. The polyolefin-soluble chromophore of any one of claims 4 to 10, wherein the components are reacted in a solvent system (single solvent or mixture of solvents) having a dielectric constant of less than 18 or 16 or 12 or 10 or 8 or 6 or 5.

12. A photovoltaic cell comprising the polyolefin-soluble chromophore of any one of claims 4 to 1 1.

13. A colorimetric marker for paper, synthetic fabric or sheets, organic or biological fluids, or natural fibers and fabrics comprising the polyolefin-soluble chromophore of any one of claims 4 to 12.

14. A catalyst for hydrophobic media comprising the polyolefin-soluble chromophore of any one of claims 4 to 13.

15. A polyolefin-soluble chromophore comprising the reaction product of a terminally functionalized polyolefin having a Mn of at least 300 g/mole having a primary linker, and a chromophore-forming moiety.

16. The polyolefin-soluble chromophore of claim 15, wherein the chromophore-forming moiety is a phthalonitrile or pyrrole.

17. A process for forming a polyolefin-soluble chromophore comprising contacting a terminally functionalized polyolefin having a Mn of at least 300 g/mole with a chromophore having a complementary functional moiety to form the polyolefin-soluble chromophore.

18. The process of claim 17, wherein the contacting results in a chemical reaction selected from esterification, etherification, amidation, amination, alkene cross-metathesis, carbon- carbon cross-coupling, elimination, addition, substitution, or combinations thereof.

19. The process of claims 17 or 18, wherein a vinyl-terminated polyolefin, comprising a vinyl group at its terminal end of the chain, is transformed to comprise a primary linker to form the functionalized polyolefin.

20. The process of any one of claims 17 - 19, wherein the polyolefin is selected from propylene-based oligomers, co-oligomers, polymers and copolymers, and ethylene-based oligomers, co-oligomers, polymers and copolymers.

21. The process of any one of claims 17 - 20, wherein the components are contacted in a solvent system (single solvent or mixture of solvents) having a dielectric constant of less than 18 or 16 or 12 or 10 or 8 or 6 or 5.

22. A process for forming a polyolefin-soluble chromophore comprising:

contacting a vinyl-terminated polyolefin with a functionalizing agent to form a terminally functionalized polyolefin comprising a primary linker;

contacting the terminally functionalized polyolefin comprising a primary linker with a chromophore having a complementary functional moiety or a chromophore-forming moiety; and

isolating the polyolefin-soluble chromophore.

23. The process of claim 22, wherein the chromophore is based on azobenzenes, phthalocyanines, porphyrins, or combinations thereof.

24. The process of claims 22 or 23, wherein the chromophore-forming moiety is based on pyrrols or mercaptoalkylacids, or combinations thereof.

25. The process of any one of claims 22 - 24, wherein the functionalizing agent is any agent capable of reacting with a vinyl group to form ester, ketone, aldehyde, carboxylate (and carboxylic acid), epoxy, anhydride, thiol, silane, hydroxyl, amine, or halogen primary linker.